Nuclear magnetic resonance microscopy studies of membrane biofouling

There is a substantial need for novel measurement techniques that enable non-invasive spatially resolved observation of biofouling in nanofiltration (NF) and reverse osmosis (RO) membrane modules. Such measurements will enhance our understanding of the key design and operational parameters influencing biofilm fouling. In this study we demonstrate the first application of nuclear magnetic resonance microscopy (NMR) to a spiral wound reverse osmosis (RO) membrane module. The presented NMR protocols allow the extraction of the evolution with biofouling of (i) the spatial biofilm distribution in the membrane module, (ii) the spatially resolved velocity field and (iii) displacement propagators, which are distributions of molecular displacement of a passive tracer (in our case, water) in the membrane. From these measurements, the effective membrane surface area is quantified. Despite the opaque nature of membrane design, NMR microscopy is shown to be able to provide a non-invasive quantitative measurement of RO membrane biofouling and its impact on hydrodynamics and mass transport. Minimal biofilm growth is observed to have a substantial impact on flow field homogeneity.     

Enhancement of detection sensitivity for indirect photometric detection of anions and cations in capillary electrophoresis

This review focuses on the indirect photometric detection of anions and cations by capillary electrophoresis. Special emphasis has been placed on the sensitivity of the technique and approaches taken to enhance detection limits. Theoretical considerations and requirements have been discussed, including buffering, detection sensitivity, separation of cations, and detector linearity. A series of tables detailing highly absorbing probes and the conditions of their use for indirect photometric detection are included.     

Synthesis and thermal decomposition of N,N-dialkoxyamides

N,N-dialkoxyamides 1c, a virtually unstudied member of the new class of anomeric amides, amides bearing two electronegative atoms at nitrogen, have been synthesised in useful yields directly from hydroxamic esters using phenyliodine(III)bis(trifluoroacetate) (PIFA). Infrared carbonyl stretch frequencies and carbonyl (13)C NMR properties have been reported, which support strong inhibition of amide resonance in these amides. Their thermal decomposition reactions in mesitylene at 155 °C proceed by homolysis to form alkoxyamidyl and alkoxyl free radicals in preference to HERON rearrangements to esters. The reactions follow first-order kinetics and for a series of N,N-dimethoxy-4-substituted benzamides, activation energies of 125-135 kJ mol(-1) have been determined together with weakly negative entropies of activation.     

Rapid measurement of transient velocity evolution using GERVAIS

Rapid velocity measurements using GERVAIS (Gradient Echo Rapid Velocity and Acceleration Imaging Sequence), an EPI (Echo Planar Imaging) based technique capable of measuring velocity over an observation time of several milliseconds, are performed on a wide-gap Couette Rheo-NMR cell for the first time. A variable delay time between a control signal to initiate a transition in flow and the start of the measurement sequence is incorporated to allow investigation of the transient evolution of the velocity field following a step change in rotation rate. Both the commencement and the cessation of imposed shear stress are investigated for (i) a shear banding micellar solution of CPyCl (cetylpyridiniumchloride)/NaSal (sodium salicylate) in brine and (ii) a low molecular weight PDMS (polydimethylsiloxane) oil. With respect to the micellar solution, an elastic shear wave is seen to propagate across the cell following the commencement of shear stress whilst an oscillatory ‘recoil’ is observed following the cessation of shear stress; neither of these phenomena were observed for the PDMS oil which exhibited a purely viscous response as expected for an incompressible Newtonian fluid. This technique has potential applications across a wide range of transient rheological investigations, particularly with respect to optically opaque materials.     

New isoelectric buffers for capillary electrophoresis: N-carboxymethylated polyethyleneimine as a macromolecular isoelectric buffer

Isoelectric buffers are attractive for electrophoresis because of their low conductivity, and their compatibility with indirect photometric detection in capillary electrophoresis (CE) where they do not interfere with the detection by exhibiting competitive displacement of the UV-absorbing probe ion. N-carboxymethylated polyethyleneimine (CMPEI) was prepared by introducing a half molar equivalent of carboxylate groups onto a polyethyleneimine backbone. Its isoelectric point determined by conductometric titration and from the pH of its dilute aqueous solution is approx. 6.8, which allows isoelectric buffering at a lower pH compared to histidine (pI7.7). Although the isoelectric point is somewhat diffuse, as expected for a polymeric compound, it exhibits a buffering capacity at a pI point of about twice that of histidine. Studies of electroosmotic flow (EOF) profile at various pH values in fused silica capillaries showed that CMPEI adsorbs onto the fused silica wall and reverses the EOF at pH < 6.5. CMPEI was applied as a buffer in an electrolyte containing 0.5 mM of the anionic dye tartrazine used as the probe for indirect detection of anions. The separation system exhibited a stable baseline, no system peaks, separation efficiencies of up to 195,000 theoretical plates, and detection limits down to 0.2 microM or 2 amol of injected analyte.     

Iodine-129 in Thyroid Glands: A Sensitive Biological Marker of Fission Product Exposure

Iodine-129 may have no radiation hazard but it is a useful marker. Animal thyroids concentrate the isotope to 4 orders of magnitude greater than the intake. This results in a potential biological and physical indicator of radioiodine contamination. Since 1943, ¹²⁹I/¹²⁷I ratio in animal thyroids from the Northern Hemisphere has increased 2 to 5 orders of magnitude. Since 1985, thyroids of deer living near a nuclear reprocessing facility have contained ¹²⁹I, which are 3 to 7 orders of magnitude greater than pre-nuclear levels. Limited measurements of ¹²⁹I in thyroids from the Southern Hemisphere have shown little increase. An appendix is presented to show that ¹²⁹I, may be helpful to evaluate past radiation hazard from fission products.     

The Role of Cytochrome P450 AbyV in the Final Stages of Abyssomicin C Biosynthesis

Abyssomicin C and its atropisomer are potent inhibitors of bacterial folate metabolism. They possess complex polycyclic structures, and their biosynthesis has been shown to involve several unusual enzymatic transformations. Using a combination of synthesis and in vitro assays we reveal that AbyV, a cytochrome P450 enzyme from the aby gene cluster, catalyses a key late-stage epoxidation required for the installation of the characteristic ether-bridged core of abyssomicin C. The X-ray crystal structure of AbyV has been determined, which in combination with molecular dynamics simulations provides a structural framework for our functional data. This work demonstrates the power of combining selective carbon-13 labelling with NMR spectroscopy as a sensitive tool to interrogate enzyme-catalysed reactions in vitro with no need for purification.     

Influence of the chemical structure of (co)polymer resists on their sensitivity to radiation

Resists operating via two mechanisms, i.e., disruption of the main chain and hydrolysis of side functional groups occurring upon EUV and electron beam irradiation, are studied as a function of the chemical composition of a polymer substrate. We show that the latter, belonging to the group of chemically amplified resists, are an order of magnitude more sensitive to radiation and possess outstanding contrast, as compared with disruptive type resists.